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JOURNAL OF APPLIED POLYMER SCIENCE · 2010 ·Vol. 117 ·期 1 ·235-242 · IF 1.203

Silk-inspired polyurethane containing GlyAlaGlyAla tetrapeptide. I. Synthesis and primary structure

Hongtao Liu,Weilin Xu,Sanping Zhao,Jingjing Huang,Hongjun Yang,Yunli Wang,Chenxi Ouyang

Biomedical polyurethane (PU) and silk fibroin have similar molecular architecture in their primary and aggregate structure, both of which have imido bonds and microphase separation, and they have been employed as scaffold materials for biomedical applications. As the featured peptide sequence of silkworm silk protein, GlyAlaGlyAla (GAGA) tetrapeptide was synthesized by using traditional liquid-phase peptide synthesis method with Boc-protected alanine and glycine as starting materials, and was transformed to its derivative with two end-amido groups. The derivative was incorporated into the backbone of the classical synthetic copolyurethane as a chain extender to form a silk-inspired polyurethane. Elemental analysis showed the nitrogen content in the silk-inspired PU was higher than that in the butanediol-extended PU but lower than the theoretical value, indicating the chain extender containing GAGA was partially incorporated into the PU chain. The results from 1 H-nuclear magnetic resonance, Fourier transform infrared spectra, Raman scattering spectra and pyrolysis-gas chromatography/mass spectrometry qualitatively identified the primary structure of the silk-inspired polyurethane. This concept and strategy may allow the fabrication of a new class of thermoplastic polyurethane elastomer to mimic the structure and properties of silk fibers if in fiber form, which combines traditional synthetic polymer chains with peptide sequences. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010

CAS / MDL: 110-63-4 25190-06-1
研究领域: 材料科学 · 生物医学工程
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FOOD CHEMISTRY · 2024 · IF 8.5

Silk protein: A novel antifungal and edible coating for strawberry preservation

Yan Wang,Weijie Wu,Ruiling Liu,Ben Niu,Xiangjun Fang,Hangjun Chen,Mohamed A. Farag,Li-Shu Wang,Guannan Wang,Hailong Yang,Huizhi Chen,Haiyan Gao

In this study, an antimicrobial component, silk protease inhibitors (SPIs), was extracted from discarded silkworm cocoons, and a suitable degumming method for obtaining regenerated silk fibroin (SF) was screened. An edible antimicrobial coating was prepared by mixing SPIs with SF for evaluation of potential in strawberries preservation. Results demonstrated that SPI could effectively inhibit mycelial growth and spore germination. The alkaline protease method exhibited the highest degumming rate of 24.4 %. The SPI-SF coating exhibited excellent mechanical properties, high water vapor permeability, and easy washability. Within 10 days, seedlings treatment with SPI-SF coating solution showed a germination rate of 94.3 %, and exhibited good biocompatibility with HepG2 cells. Coating with SPI-SF led to increase in the storage period of strawberries to 10–14 days, concurrent with considerable reduction in decay rate at room temperature. Conclusively, this study demonstrates the potential of SPI-SF edible coating in strawberries preservation.

研究领域: 食品科学 · 材料科学 · 农业科学 · 生物技术
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ACS Applied Materials & Interfaces · 2022 · IF 10.383

Molecular Design and Preparation of Protein-Based Soft Ionic Conductors with Tunable Properties

Xin Yu,Yang Hu,Haoyuan Shi,Ziyang Sun,Jinghang Li,Haoran Liu,Hao Lyu,Jiujie Xia,Jingda Meng,Xingyu Lu,Jingjie Yeo,Qiyang Lu,Chengchen Guo

Protein-based soft ionic conductors have attracted considerable research interest in recent years with great potential in applications at the human–machine interfaces. However, a fundamental mechanistic understanding of the ionic conductivity of silk-based ionic conductors is still unclear. Here, we first developed an environmental-friendly and scalable method to fabricate silk-based soft ionic conductors using silk proteins and calcium chloride. The mechanistic understanding of the ion transport and molecular interactions between calcium ions and silk proteins at variable water contents was investigated in-depth by combining experimental and simulation approaches. The results show that calcium ions primarily interact with amide groups in proteins at a low water content. The ionic conductivity is low since the calcium ions are confined around silk proteins within 2.0–2.6 Å. As water content increases, the calcium ions are hydrated with the formation of water shells, leading to the increased distance between calcium ions and silk proteins (3.3–6.0 Å). As a result, the motion of the calcium ions increased to achieve a higher ionic conductivity. By optimizing the ratio of the silk proteins, calcium ions, and water, silk-based soft ionic conductors with good stretchability and self-healing properties can be obtained. Such protein-based soft ionic conductors can be further used to fabricate smart devices such as electrochromic devices.

研究领域: 材料科学 · 生物物理学
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Advanced Fiber Materials · 2022 ·Vol. 4 ·期 3 ·448-456 · IF 12.958

Effect of Microwave Irradiation on Dipeptides and Proteins Derived from Silk During Solvation

Li Na,Ma Ying,Chen Niuniu,Tang Xiaoyu,Lv Shanshan

Silkworm silk and spider silk have been attracting numerous interests. Rapid solvation of silkworm silk protein and spider silk protein without hydrolysis of peptide bonds is highly desirable. Microwave irradiation has been proposed for facile extraction of water-soluble silk protein by various liquid media. However, microwave exposure can cause hydrolysis of peptide bonds, leading to irreversible degradation of silk protein. In this study, a series of representative dipeptides and a rationally designed recombinant protein derived from silk protein is employed to investigate the effect of microwave on the stability of the peptide bonds during a long time dissolution process, i.e., heating at 60 ℃ in a CaCl 2 :CH 3 CH 2 OH:H 2 O (1:2:8) solution. Results demonstrate that microwave irradiation imposes a minor damage and a negligible cleavage of the peptide bonds, compared with the conventional heating method. The microwave irradiation treatment suggested in this is suitable for dissolution of silk protein. It is anticipated that this approach can be developed to a commercial level commercially.  Graphical abstract

研究领域: 生物化学 · 材料科学
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JOURNAL OF RARE EARTHS · 2020 · IF 3.104

Evaluation of biological effects of three neodymium compounds on silkworm, Bombyx mori

Vivian Andoh,Huaiyang Guan,Lin Ma,Weiguo Zhao,Long Li,Guohua Wu

Neodymium (Nd) is one of the most famous members of rare earth elements family. With the increasing global demand for Nd, it can inevitably enter the environment and affect the ecological environment through the food chain and other ways. Therefore, it is very important to study the biological effects of Nd. In this study, the biological effects of 3 kinds of Nd compounds, i.e. neodymium oxide (Nd 2 O 3 ), neodymium chloride (NdCl 3 ) and neodymium nitrate (Nd(NO 3 ) 3 ), were evaluated by using silkworm models through the method of intravascular injection. Each of the three Nd compounds was prepared into 6 groups at different concentrations (40, 50, 60, 70, 80, 90 μg/μL). The results show that within the certain concentration range, Nd compounds show great damage to the growth of silkworms since high death rate is observed: the death rate from Nd 2 O 3 group is floating between 30% and 80%, the one from NdCl 3 group is between 17% and 33% and that from Nd(NO 3 ) 3 group is between 23% and 37%. It also reveals that Nd compounds have some negative effects on the body length and weight of silkworms. However, the histophysiological study shows that the three Nd compounds cause no obvious negative effects on the cell morphologies in midgut, fat body and silk gland. The XRD and FTIR spectra show that the secondary and the crystalline structures of silks are not destroyed, the TGA and DTG data exhibit that the thermal stability of silks is not damaged, and the tensile test shows that the mechanical properties of silks are not affected significantly by the intake of Nd compounds. In general, the intake of Nd compounds has significant inhibitory effects on silkworm growth but little negative impact on silk structures or cell morphology, the study can provide useful toxicological data for the safe application of Nd compounds in various fields.

研究领域: 环境科学 · 生物学
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INDUSTRIAL CROPS AND PRODUCTS · 2022 · IF 6.449

The conversion of castor oil to a series of functional polyamides inspired by natural silks

Juan He,Lingzhi Song,Zhongkai Wang

The design of functional polyamides for specialized applications has attracted increasing attention during recent years. Herein, a facile and efficient method towards mechanical strong functional polyamides with varied side groups is developed. An α , ω -diene functional amide monomer was prepared through the amidation reaction of methyl 10-undecenoate (a kind of castor oil derivative) and 1,3-diamino-2-propanol. The pendant hydroxyl group was converted to ester groups to afford six other monomers. High molecular weight functional polyamides with varied pendant groups, including hydroxyl, acetate, butyrate , isobutyrate, benzoate, acrylate, and imidazole, were prepared via thiol-ene addition polymerization. Differential scanning calorimetry (DSC) and atomic force microscopy (AFM) results indicate that the melting temperature, degree of crystallization, and crystalline size depend on the pendant groups. Inspired by natural silk proteins , functional polyamides with controllable mechanical properties can be achieved by copolymerizing of these monomers.

研究领域: 材料科学 · 有机化学
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RSC Advances · 2020 ·Vol. 10 ·期 47 ·28408-28414 · IF 3.119

Inventing a facile method to construct Bombyx mori (B. mori) silk fibroin nanocapsules for drug delivery

Heming Zheng,Bo Duan,Zheyu Xie,Jie Wang,Mingying Yang

Bombyx mori (B. mori) silk fibroin (SF) microcapsules have acted as a great candidate in delivering drugs. However, it is difficult to fabricate SF nanocapsules using the present layer-by-layer (LBL) technique. In addition, the current SF microcapsules have limits in loading negatively charged drugs. Here, we invent a novel LBL method by introducing silane (APTES) as a structure indicator to produce SF nanocapsules that can load drugs with negative or positive charge. LBL assembly was completed by alternately coating SF and APTES on the template of polystyrene (PS) nanospheres by electrostatic attraction. SF nanocapsules were obtained after removal of the PS templates. Zeta potential analysis proved LBL assembly was indeed driven by the interaction between negative charge of SF and positive charge of APTES. Fluorescence images and electric microscope images indicated that SF nanocapsules had a hollow and stable structure with diameter at nearly 250 nm. The highest encapsulation rate of DOX or Ce6 were up to 80% and 90%, respectively, indicating SF nanocapsules have a high loading capability for both cationic and anionic drugs. In vitro cell experiments proved the biocompatibility of SF nanocapsules and their burst drug release in response to acidic environment. Furthermore, chemotherapy and photodynamic therapy proved SF nanocapsules loaded with DOX or Ce6 had significant inhibition on tumor cells. Our results suggested that this LBL technique is a facile method for polymers with negative charge to fabricate nanocapsules for antitumor drug carrier.

研究领域: 生物材料学 · 药物递送系统 · 肿瘤治疗
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Journal of Materials Chemistry B · 2015 ·Vol. 3 ·期 31 ·6509-6519 · IF 4.726

Incorporation of quantum dots into silk biomaterials for fluorescence imaging

Z. Z. Zheng,M. Liu,S. Z. Guo,J. B. Wu,D. S. Lu,G. Li,S. S. Liu,X. Q. Wang,D. L. Kaplan

Tracking the distribution and degradation of biomaterials after in vivo implantation or injection is important for tissue engineering and drug delivery. Intrinsic and externally labeled fluorescence has been widely used for these purposes. In the present study, 3-mercaptopropionic acid (MPA)-coated CdTe quantum dots (QDs) were incorporated into silk materials via strong interactions between QDs and silk, likely involving the hydrophobic beta-sheet structures in silk. MPA-QDs were pre-mixed with silk solution, followed by ultrasonication to induce silk gelation or by blending with polyvinyl alcohol (PVA) to generate silk microspheres. Silk structural changes and hydrogel/microsphere morphologies were examined by ATR-FTIR and SEM, respectively. The fluorescence of QD-incorporated silk hydrogels and microspheres remained stable in PBS pH 7.4 for more than 4 days. The amount of QDs released from the materials during the incubation was dependent on loading; no QDs were released when loading was below 0.026 nmol mg−1 of silk. After subcutaneous injection into mice, the fluorescence of QD-incorporated silk microspheres was quenched within 24 h, similar to that of free QDs. In contrast, the QD-incorporated silk hydrogels fluoresced for more than 4 days in vivo.

CAS / MDL: 7550-35-8
研究领域: 生物医学工程 · 材料科学
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Biomaterials Science · 2017 ·Vol. 5 ·期 7 ·1279-1292 · IF 4.21

DNA preservation in silk

Yawen Liu,Zhaozhu Zheng,He Gong,Meng Liu,Shaozhe Guo,Gang Li,Xiaoqin Wang,David L. Kaplan

The structure of DNA is susceptible to alterations at high temperature and on changing pH, irradiation and exposure to DNase. Options to protect and preserve DNA during storage are important for applications in genetic diagnosis, identity authentication, drug development and bioresearch. In the present study, the stability of total DNA purified from human dermal fibroblast cells, as well as that of plasmid DNA, was studied in silk protein materials. The DNA/silk mixtures were stabilized on filter paper (silk/DNA + filter) or filter paper pre-coated with silk and treated with methanol (silk/DNA + PT-filter) as a route to practical utility. After air-drying and water extraction, 50–70% of the DNA and silk could be retrieved and showed a single band on electrophoretic gels. 6% silk/DNA + PT-filter samples provided improved stability in comparison with 3% silk/DNA + filter samples and DNA + filter samples for DNA preservation, with ∼40% of the band intensity remaining at 37 °C after 40 days and ∼10% after exposure to UV light for 10 hours. Quantitative analysis using the PicoGreen assay confirmed the results. The use of Tris/borate/EDTA (TBE) buffer enhanced the preservation and/or extraction of the DNA. The DNA extracted after storage maintained integrity and function based on serving as a functional template for PCR amplification of the gene for zinc finger protein 750 (ZNF750) and for transgene expression of red fluorescence protein (dsRed) in HEK293 cells. The high molecular weight and high content of a crystalline beta-sheet structure formed on the coated surfaces likely accounted for the preservation effects observed for the silk/DNA + PT-filter samples. Although similar preservation effects were also obtained for lyophilized silk/DNA samples, the rapid and simple processing available with the silk–DNA–filter membrane system makes it appealing for future applications.

CAS / MDL: 7550-35-8
研究领域: 遗传学 · 生物技术 · 材料科学
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SAUDI JOURNAL OF BIOLOGICAL SCIENCES · 2022 · IF 4.052

Apoptotic and antiproliferative effects of silk protein sericin conjugated-AgNO3 nanoparticles in human breast cancer cells

Samaira Mumtaz,Shaukat Ali,Asim Pervaiz,Muhammad Zahid Qureshi,Kinzah Kanwal,Talha Saleem

Bombyx mori silk sericin is a globular-like protein that is used as an antioxidant, antibacterial, and antitumor agent. In this current research, we isolated sericin by degumming process and formation of sericin-AgNO 3 NPs confirmed by UV–vis spectra, SEM, EDX, FTIR, and XRD patterns. The sericin and sericin-AgNO 3 NPs mediated changes in human breast cancer cells were determined. The antiproliferative activity of sericin-AgNO 3 NPs was analyzed by MTT dye reduction assay. Alterations at molecular levels were investigated by qRT-PCR, while apoptotic effects were studied by nuclear DNA staining. After 72 h treatment, sericin and sericin-AgNO 3 NPs showed significant antiproliferative effects in MDA-MB-231 (26 %) and MCF-7 (41 %) cells. Expression modification showed prominent stimulation of cell cycle arrest and stress related genes such as cyclin-dependent kinase inhibitors (CDKN1A, CDKN1B), and GADD family genes. RT-PCR results of the GADD family include GADD45A, B, G, 34, 153 and cyclin-dependent kinase inhibitors (CDKN1A, 1B) showed pronounced induction of 3.1 to 19.8-folds in MCF-7 cell line while induction in MDA-MB-231 cell line was 2.5 to 34.3-folds. Nuclear DAPI staining showed significant induction of apoptosis and nuclear fragmentation in MDA-MB-231 cells at a concentration of 1 mg/mL for both sericin and sericin-AgNO 3 NPs. Meanwhile, in case of MCF-7 cells, after treatment with sericin and sericin-AgNO 3 NPs (1 mg/mL), the cells changed into a round shape and lost their original spindle outlook in dose-dependent manners. We concluded that sericin-AgNO 3 NPs have significant antiproliferative, apoptosis, and genetic profiling effects in both breast cancer cell lines at the highest concentration.

CAS / MDL: 7761-88-8
研究领域: 生物化学 · 肿瘤学 · 纳米医学
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Smart Medicine · 2024 ·Vol. 3 ·期 3 ·e20240027 · IF 0

Polymeric silk fibroin hydrogel as a conductive and multifunctional adhesive for durable skin and epidermal electronics

Fanfan Fu,Changyi Liu,Zhenlin Jiang,Qingyu Zhao,Aining Shen,Yilun Wu,Wenyi Gu

Silk fibroin (SF)-based hydrogels are promising multifunctional adhesive candidates for real-world applications in tissue engineering, implantable bioelectronics, artificial muscles, and artificial skin. However, developing conductive SF-based hydrogels that are suitable for the micro-physiological environment and maintain their physical and chemical properties over long periods of use remains challenging. Herein, we developed an ion-conductive SF hydrogel composed of glycidyl methacrylate silk fibroin (SilMA) and bioionic liquid choline acylate (ChoA) polymer chains, together with the modification of acrylated thymine (ThyA) and adenine (AdeA) functional groups. The resulting polymeric ion-conductive SF composite hydrogel demonstrated high bioactivity, strong adhesion strength, good mechanical compliance, and stretchability. The formed hydrogel network of ChoA chains can coordinate with the ionic strength in the micro-physiological environment while maintaining the adaptive coefficient of expansion and stable mechanical properties. These features help to form a stable ion-conducting channel for the hydrogel. Additionally, the hydrogel network modified with AdeA and ThyA, can provide a strong adhesion to the surface of a variety of substrates, including wet tissue through abundant hydrogen bonding. The biocompatible and ionic conductive SF composite hydrogels can be easily prepared and incorporated into flexible skin or epidermal sensing devices. Therefore, our polymeric SF-based hydrogel has great potential and wide application to be an important component of many flexible electronic devices for personalized healthcare.

研究领域: 生物材料 · 组织工程 · 柔性电子器件
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INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES · 2024 ·Vol. 25 ·期 12 ·6653 · IF 4.9

Hydrophilicity and Pore Structure Enhancement in Polyurethane/Silk Protein–Bismuth Halide Oxide Composite Films for Photocatalytic Degradation of Dye

Lingxi Meng,Jian Jian,Dexing Yang,Yixiao Dan,Weijie Sun,Qiuhong Ai,Yusheng Zhang,Hu Zhou

Polyurethane/silk protein–bismuth halide oxide composite films were fabricated using a blending-wet phase transformationin situsynthesis method. The crystal structure, micromorphology, and optical properties were conducted using XRD, SEM, and UV-Vis DRS characterize techniques. The results indicated that loaded silk protein enhanced the hydrophilicity and pore structure of the polyurethane composite films. The active species BiOX were observed to grow as nanosheets with high dispersion on the internal skeleton and silk protein surface of the polyurethane–silk protein film. The photocatalytic efficiency of BiOX/PU-SF composite films was assessed through the degradation of Rhodamine B under visible light irradiation. Among the tested films, the BiOBr/PU-SF composite exhibited the highest removal rate of RhB at 98.9%, surpassing the removal rates of 93.7% for the BiOCl/PU-SF composite and 85.6% for the BiOI/PU-SF composite. Furthermore, an active species capture test indicated that superoxide radical (•O2−) and hole (h+) species played a predominant role in the photodegradation process.

研究领域: 材料科学 · 环境科学
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